Quaternary surfactants

ABSTRACT

Quaternary surfactants of the formula (I), 
     
       
         
         
             
             
         
       
     
     wherein R 1 CO is a linear or branched, saturated or unsaturated, optionally hydroxy-functionalized acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R 2  is a CH 2 COOH radical, an alkyl radical having 1 to 4 carbon atoms, a CH 2 CH 2 OH or a CH 2 CH 2 OCH 2 CH 2 OH group, and X is halide, alkyl sulfate, alkyl carbonate or alkyl phosphate, are useful as surfactants in cosmetic and pharmaceutical preparations. Aqueous solutions above 50% by weight of the surfactants are flowable and pumpable.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 10/472,668,filed on Sep. 22, 2003, which was the national phase filing under 35U.S.C. § 371 of PCT International Application No. PCT/EP02/02611 whichhas an International filing date of Mar. 9, 2002, which designated theUnited States of America and which claims priority from German PatentApplication number 101 13 334.0, filed Mar. 20, 2001, the entirecontents of each of which are hereby incorporated herein by reference.

FIELD OF THE INVENTION

The invention is in the fields of cosmetics and detergents and relatesto novel surfactants with a betaine or amide quat structure, toprocesses for the preparation thereof, and to their use for thepreparation of surface-active compositions.

BACKGROUND INFORMATION

Surface-active substances with quaternary centers are divided roughlyinto amphoteric or zwitterionic surfactants on the one hand and cationicsurfactants on the other hand. For both groups, there are countlessexamples in the market, such as, for example, the reaction products offatty acid amidopropylamine with sodium chloroacetate (known under theINCI name Cocamidopropyl Betaine) or the alkylation products oftriethanolamine fatty acid esters (known under the name ester quats). Acommon feature of these substances is their ability to attach to solid,especially negatively charged, surfaces, which is utilized, for example,for hand modifiers and hair-treatment compositions. Although the knownproducts exhibit a performance which is in principle entirelysatisfactory, there is still a desire for improved properties for anumber of special applications. These include, in particular, thetechnically simple availability of concentrates with high storagestability.

Consequently, it was the object of the present invention to providenovel betaines or ester quats which, even at solids contents above 50%by weight, are flowable and pumpable, preferably have a Brookfieldviscosity (20° C., spindle 1, 10 rpm) of less than 10 000 mPas and inparticular less than 6 000 mPas. At the same time, the concentratesshould neither gel nor change to a noteworthy degree with regard totheir viscosity, even after storage at 40° C. for several weeks.Finally, it was desired to provide concentrates for various applicationswhich are transparent even after prolonged storage under temperature.The demand for excellent biodegradability and dermatologicalcompatibility represents a permanent requirement.

DESCRIPTION OF THE INVENTION

The invention provides quaternary surfactants of the formula (I),

in which R¹CO is a linear or branched, saturated or unsaturated,optionally hydroxy-functionalized acyl radical having 6 to 22 carbonatoms and 0, 1, 2 or 3 double bonds, R² is a CH₂COOH radical or an alkylradical having 1 to 4 carbon atoms, a CH₂CH₂OH or CH₂CH₂OCH₂CH₂OH groupand X is halide, alkyl sulfate, alkyl carbonate or alkyl phosphate. Thequaternary surfactants can here have either a betaine or amide quatstructure, depending on the alkylating agent.

Surprisingly, it has been found that the novel surfactants can beadjusted to solids contents above 50% by weight without the addition ofauxiliaries, such as, for example, (hydroxy)carboxylic acids, andnevertheless remain flowable and pumpable. In addition, even duringstorage under temperature, neither gelation nor collapse of theviscosity is observed. The concentrates are also transparent,particularly when dicarboxylic acids have been condensed into themolecule. The products are additionally completely biodegradable and aretolerated by the skin to an excellent degree.

The invention further provides a process for the preparation ofquaternary surfactants of the formula (I),

in which R¹CO is a linear or branched, saturated or unsaturated,optionally hydroxy-functionalized acyl radical having 6 to 22 carbonatoms and 0, 1, 2 or 3 double bonds, R² is a CH₂COOH radical or an alkylradical having 1 to 4 carbon atoms, a CH₂CH₂OH or CH₂CH₂OCH₂CH₂OH groupand X is halide, alkyl sulfate, alkyl carbonate or alkyl phosphate,which is characterized in that

-   (a) fatty acids and/or fatty acid glycerol esters are condensed with    aminopropylmethylethanolamine, and-   (b) the resulting fatty acid amidoamines are then quaternized with    alkylating agents in a manner known per se.

Amidoamine Formation

Both for the betaines according to the invention and also for the amidequats, the amidoamines represent the common intermediates, which takesplace either by amidation of the fatty acids or transamidation of thefatty acid glycerol esters, specifically the triglycerides, withaminopropylmethylethanolamine (APMEA). Suitable starting materials forthe amidation are fatty acids of the formula (II)

R¹CO—OH  (II)

in which R¹CO has the meaning described above. Typical examples thereofare caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,lauric acid, isotridecanoic acid, myristic acid, palmitic acid,palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselic acid, linoleic acid, linolenic acid, ricinoleic acid,12-hydroxystearic acid, elaeostearic acid, arachidic acid, gadoleicacid, behenic acid, and erucic acid, and technical-grade mixturesthereof which are produced, for example, during the pressurized cleavageof natural fats and oils, during the reduction of aldehydes from theRoelen oxo synthesis or the dimerization of unsaturated fatty acids.Preference is given to technical-grade fatty acids having 12 to 18carbon atoms, such as, for example, coconut, palm, palm kernel or tallowfatty acid. In place of the fatty acids, it is also possible for fattyacid glycerol esters which conform to the formula (III) to betransamidated:

R¹CO—CH₂CH(OR³)CH₂OR⁴  (III)

Here, R¹CO has the meaning given above, while R³ and R⁴, independentlyof one another, are hydrogen or optionally hydroxy-functionalized acylradicals having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.Preferably, R³ and R⁴ are also acyl radicals, i.e. the fatty acidglycerol esters are natural or synthetic triglycerides, i.e. fats oroils, such as, for example, coconut oil, palm oil, palm kernel oil,olive oil, olive kernel oil, rapeseed oil, sunflower oil, groundnut oil,linseed oil, beef tallow or pork lard. It is likewise possible to carryout the condensation of the fatty acids or glycerides with the APMEA inthe presence of defined amounts of dicarboxylic acids, such as, forexample, oxalic acid, malonic acid, succinic acid, maleic acid, fumaricacid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaicacid, sebacic acid and/or dodecanedioic acid. This method results in apartially oligomeric structure of the betaines or amide quats, which hasa particularly advantageous effect on the solubility of the products toform clear solutions, particularly when adipic acid is co-used.Typically, the ratio of the free carboxylic acid groups betweenmonocarboxylic acid and dicarboxylic acid is 90:10 to 80:20.

To prepare the fatty acid amidoamines, the fatty acids or fatty acidglycerol esters and the APMEA can be used in the molar ratio from 1.1:1to 3:1. With regard to the performance properties of the resultingbetaines or amide quats, a feed ratio of from 1.2:1 to 2.2:1, preferably1.5:1 to 1.9:1, has proven particularly advantageous. The preferredfatty acid amidoamines are technical-grade mixtures of mono-, di- andtriamides with an average degree of amidation of from 1.5 to 1.9. Thecondensation can be carried out in a manner known per se, i.e. in thepresence of phosphorus or hypophosphorous acid as catalyst, and withremoval of the water of condensation from the reaction equilibrium.Typically, the reaction is carried out at temperatures in the range from150 to 200° C. over a period of from 2 to 8 h. For performance reasons,it is, moreover, advisable to remove free unreacted amine under reducedpressure in order that the intermediate is odorless and subsequentirritations are prevented.

Quaternization

The quaternization of the intermediates is an alkylation which leads tobetaines or amide quats, depending on the alkylating agent. In the firstcase, suitable alkylating agents are chloroacetic acid and/or saltsthereof, specifically sodium chloroacetate, and in the second case,suitable alkylating agents are alkyl halides, dialkyl sulfates,carbonates or phosphates, preferably methyl chloride, dimethyl sulfateor dimethyl carbonate. Alternatively, the quaternization can also becarried out with ethylene oxide. While the betainization is usuallycarried out in aqueous solution, the quaternization is usually carriedout in alcoholic solution, preferably in ethanol, isopropyl alcohol orpropylene glycol. The amount of quaternizing agent will usually bemeasured such that in all cases a small stoichiometric excess ispresent. Particularly when dimethyl sulfate is used, a small deficit isadvisable in order to ensure that no traces of the alkylating agentremain in the end-product. In some cases, a thermal aftertreatment isadvisable. The molar ratio of amidoamine to alkylating agent istherefore usually 1:0.95 to 1:1.05. The betainization or quaternizationis usually carried out at temperatures in the range from 50 to 90° C.over a period of from 2 to 10 h.

INDUSTRIAL APPLICABILITY

The novel surfactants are characterized by typical amphoteric orcationic properties, i.e. attach to solid, especially negativelycharged, surfaces. Further subject-matters of the invention thereforerelate to their use for the preparation of cosmetic and/orpharmaceutical preparations, and also of laundry detergents, dishwashingdetergents, cleaners and hand modifiers in which they may be present inamounts of from 1 to 30% by weight, preferably 5 to 25% by weight and inparticular 10 to 15% by weight.

Cosmetic and/or Pharmaceutical Preparations

The surface-active preparations which comprise the novel surfactants arepreferably skin- or hair-treatment compositions which can likewise havefurther auxiliaries and additives typical for these compositions. Theseinclude, for example, mild surfactants, oily bodies, emulsifiers,pearlescent waxes, bodying agents, thickeners, superfatting agents,stabilizers, polymers, silicone compounds, fats, waxes, lecithins,phospholipids, biogenic active ingredients, UV light protection factors,antioxidants, deodorants, antiperspirants, antidandruff agents, filmformers, swelling agents, insect repellents, self-tanning agents,tyrosine inhibitors (depigmentation agents), hydrotropic agents,solubilizers, preservatives, perfume oils, dyes and the like.

Surfactants

Surface-active substances which may be present are anionic, nonionic,cationic and/or amphoteric or amphoteric surfactants, the content ofwhich in the compositions is usually about 1 to 70% by weight,preferably 5 to 50% by weight and in particular 10 to 30% by weight.Typical examples of anionic surfactants are soaps,alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ethersulfonates, glycerol ether sulfonates, α-methyl ester sulfonates,sulfo-fatty acids, alkyl sulfates, fatty alcohol ether sulfates,glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ethersulfates, monoglyceride (ether) sulfates, fatty acid amide (ether)sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylicacids and salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids, such as, forexample, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acidcondensates (in particular wheat-based vegetable products) and alkyl(ether) phosphates. If the anionic surfactants contain polyglycol etherchains, these can have a conventional homolog distribution, butpreferably have a narrowed homolog distribution. Typical examples ofnonionic surfactants are fatty alcohol polyglycol ethers, alkylphenolpolyglycol ethers, fatty acid polyglycol esters, fatty acid amidepolyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers or mixed formals, optionally partiallyoxidized alk(en)yl oligoglycosides or glucoronic acid derivatives, fattyacid N-alkylglucamides, protein hydrolysates (in particular wheat-basedvegetable products), polyol fatty acid esters, sugar esters, sorbitanesters, polysorbates and amine oxides. If the nonionic surfactantscontain polyglycol ether chains, these can have a conventional homologdistribution, but preferably have a narrowed homolog distribution.Typical examples of cationic surfactants are quaternary ammoniumcompounds, such as, for example, dimethyldistearylammonium chloride, andester quats, in particular quaternized fatty acid trialkanolamine estersalts. Typical examples of amphoteric or zwitterionic surfactants arealkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates,imidazoliniumbetaines and sulfobetaines. Said surfactants areexclusively known compounds. With regard to structure and preparation ofthese substances, reference may be made to relevant review works, forexample, J. Falbe (ed.), “Surfactants in Consumer Products”, SpringerVerlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), “Katalysatoren,Tenside und Mineralöladditive”, Thieme Verlag, Stuttgart, 1978, pp.123-217. Typical examples of particularly suitable mild, i.e.particularly skin-compatible surfactants are fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines, amphoacetals and/or protein fatty acid condensates,the latter preferably based on wheat proteins.

Oily Bodies

Suitable oily bodies are, for example, Guerbet alcohols based on fattyalcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters oflinear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcoholsand/or esters of branched C₆-C₁₃-carboxylic acids with linear orbranched C₆-C₂₂-fatty alcohols, such as, for example, myristylmyristate, myristyl palmitate, myristyl stearate, myristyl isostearate,myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate,cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetylbehenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearylstearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearylerucate, isostearyl myristate, isostearyl palmitate, isostearylstearate, isostearyl isostearate, isostearyl oleate, isostearylbehenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleylstearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenylisostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucylmyristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyloleate, erucyl behenate and erucyl erucate. Also suitable are esters oflinear C₆-C₂₂-fatty acids with branched alcohols, in particular2-ethylhexanol, esters of C₁₈-C₃₈-alkyl hydroxycarboxylic acids withlinear or branched C₆-C₂₂-fatty alcohols (cf. DE 19756377 A1), inparticular dioctyl malates, esters of linear and/or branched fatty acidswith polyhydric alcohols (such as, for example, propylene glycol,dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides basedon C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based onC₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbetalcohols with aromatic carboxylic acids, in particular benzoic acid,esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcoholshaving 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2to 6 hydroxyl groups, vegetable oils, branched primary alcohols,substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcoholcarbonates, such as, for example, dicaprylyl carbonate (Cetiol® CC),Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8to 10, carbon atoms, esters of benzoic acid with linear and/or branchedC₆-C₂₂-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical orunsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkylgroup, such as, for example, dicaprylyl ether (Cetiol® OE), ring-openingproducts of epoxidized fatty acid esters with polyols, silicone oils(cyclomethicones, silicon methicone types, inter alia) and/or aliphaticor naphthenic hydrocarbons, such as, for example, such as squalane,squalene or dialkylcyclohexanes under consideration.

Emulsifiers

Suitable emulsifiers are, for example, nonionogenic surfactants from atleast one of the following groups;

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or 0        to 5 mol of propylene oxide to linear fatty alcohols having 8 to        22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to        alkylphenols having 8 to 15 carbon atoms in the alkyl group, and        alkylamines having 8 to 22 carbon atoms in the alkyl radical;    -   alkyl and/or alkenyl oligoglycosides having 8 to 22 carbon atoms        in the alk(en)yl radical and the ethoxylated analogs thereof;    -   addition products of from 1 to 15 mol of ethylene oxide to        castor oil and/or hydrogenated castor oil;    -   addition products of from 15 to 60 mol of ethylene oxide to        castor oil and/or hydrogenated castor oil;    -   partial esters of glycerol and/or sorbitan with unsaturated,        linear or saturated, branched fatty acids having 12 to 22 carbon        atoms and/or hydroxycarboxylic acids having 3 to 18 carbon        atoms, and the adducts thereof with 1 to 30 mol of ethylene        oxide;    -   partial esters of polyglycerol (average degree of        self-condensation 2 to 8), polyethylene glycol (molecular weight        400 to 5 000), trimethylolpropane, pentaerythritol, sugar        alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl        glucoside, butyl glucoside, lauryl glucoside), and        polyglucosides (e.g. cellulose) with saturated and/or        unsaturated, linear or branched fatty acids having 12 to 22        carbon atoms and/or hydroxycarboxylic acids having 3 to 18        carbon atoms, and the adducts thereof with 1 to 30 mol of        ethylene oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol as in German Patent 1165574 and/or mixed esters of        fatty acids having 6 to 22 carbon atoms, methylglucose and        polyols, preferably glycerol or polyglycerol,    -   mono-, di- and trialkyl phosphates, and mono-, di- and/or        tri-PEG alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane-polyalkyl-polyether copolymers and corresponding        derivatives;    -   block copolymers, e.g. polyethylene glycol-30        dipolyhydroxystearates;    -   polymer emulsifiers, e.g. Pemulen grades (TR-1, TR-2) from        Goodrich;    -   polyalkylene glycols, and    -   glycerol carbonate.

Ethylene Oxide Addition Products

The addition products of ethylene oxide and/or of propylene oxide tofatty alcohols, fatty acids, alkylphenols or to castor oil are known,commercially available products. These are homolog mixtures whoseaverage degree of alkoxylation corresponds to the ratio of the amountsof substance of ethylene oxide and/or propylene oxide and substrate withwhich the addition reaction is carried out. C_(12/18)-fatty acid mono-and diesters of addition products of ethylene oxide to glycerol areknown from German Patent 2024051 as refatting agents for cosmeticpreparations.

Alkyl and/or Alkenyl Oligoglycosides

Alkyl and/or alkenyl oligoglycosides, their preparation and their useare known from the prior art. They are prepared, in particular, byreacting glucose or oligo-saccharides with primary alcohols having 8 to18 carbon atoms. With regard to the glycoside radical, bothmonoglycosides, in which a cyclic sugar radical is glycosidically bondedto the fatty alcohol, and also oligomeric glycosides having a degree ofoligomerization of up to, preferably, about 8, are suitable. The degreeof oligomerization here is a statistical average value which is based ona homolog distribution customary for such technical-grade products.

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride, and thetechnical-grade mixtures thereof which may also comprise small amountsof triglyceride as a minor product of the preparation process. Likewisesuitable are addition products of 1 to 30 mol, preferably 5 to 10 mol,of ethylene oxide to said partial glycerides.

Sorbitan Esters

Sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate, and technical-grade mixturesthereof. Likewise suitable are addition products of from 1 to 30 mol,preferably 5 to 10 mol, of ethylene oxide to said sorbitan esters.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are polyglyceryl-2dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3 diisostearate(Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34),polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate(Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450),polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate(Polyglycerol Caprate T2010/90) polyglyceryl-3 cetyl ether (Chimexane®NL), polyglyceryl-3 distearate (Cremophor® GS 32) and polyglycerylpolyricinoleate (Admul® WOL 1403), polyglyceryl dimerate isostearate,and mixtures thereof. Examples of further suitable polyol esters are themono-, di- and triesters, optionally reacted with 1 to 30 mol ofethylene oxide, of trimethylolpropane or pentaerythritol with lauricacid, coconut fatty acid, tallow fatty acid, palmitic acid, stearicacid, oleic acid, behenic acid and the like.

Anionic Emulsifiers

Typical anionic emulsifiers are aliphatic fatty acids having 12 to 22carbon atoms, such as, for example, palmitic acid, stearic acid orbehenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, suchas, for example, azelaic acid or sebacic acid.

Amphoteric and Cationic Emulsifiers

Furthermore, zwitterionic surfactants can be used as emulsifiers. Theterm “zwitterionic surfactants” refers to those surface-active compoundswhich carry at least one quaternary ammonium group and at least onecarboxylate and one sulfonate group in the molecule. Particularlysuitable zwitterionic surfactants are the so-called betaines, such asN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each case 8to 18 carbon atoms in the alkyl or acyl group, andcocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Particularpreference is given to the fatty acid amide derivative known under theCTFA name Cocamidopropyl Betaine. Likewise suitable emulsifiers areampholytic surfactants. The term “ampholytic surfactants” means thosesurface-active compounds which, apart from a C_(8/18)-alkyl or -acylgroup, contain at least one free amino group and at least one —COOH or—SO₃H group in the molecule and are capable of forming internal salts.Examples of suitable ampholytic surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids having in each case about 8 to 18 carbon atoms in the alkyl group.Particularly preferred ampholytic surfactants areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC_(12/18)-acylsarcosine. Finally, cationic surfactants are also suitableas emulsifiers, those of the ester quat type, preferablymethyl-quaternized difatty acid triethanolamine ester salts, beingparticularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids, suitable waxes are inter alia natural waxes, suchas, for example, candelilla wax, carnauba wax, japan wax, esparto grasswax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricurywax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax),uropygial grease, ceresin, ozokerite (earth wax), petrolatum, paraffinwaxes, microcrystalline waxes; chemically modified waxes (hard waxes),such as, for example, montan ester waxes, sasol waxes, hydrogenatedjojoba waxes, and synthetic waxes, such as, for example, polyalkylenewaxes and polyethylene glycol waxes. In addition to the fats, suitableadditives are also fat-like substances, such as lecithins andphospholipids. The term lecithins is understood by the person skilled inthe art as meaning those glycerophospholipids which are founded fromfatty acids, glycerol, phosphoric acid and choline by esterification.Lecithins are thus also often known as phosphatidylcholines (PC) in thespecialist world. Examples of natural lecithins which may be mentionedare the cephalins, which are also referred to as phosphatidic acids, andderivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast,phospholipids are usually understood as meaning mono- and preferablydiesters of phosphoric acid with glycerol (glycerol phosphates), whichare generally classed as fats. In addition, sphingosines orsphingolipids are also suitable.

Pearlescent Waxes

Examples of suitable pearlescent waxes are: alkylene glycol esters,specifically ethylene glycol distearate; fatty acid alkanolamides,specifically coconut fatty acid diethanolamide; partial glycerides,specifically stearic acid monoglyceride; esters of polybasic, optionallyhydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22carbon atoms, specifically long-chain esters of tartaric acid; fattysubstances, such as, for example, fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates, which have a total of atleast 24 carbon atoms, specifically laurone and distearyl ether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid,ring-opening products of olefin epoxides having 12 to 22 carbon atomswith fatty alcohols having 12 to 22 carbon atoms and/or polyols having 2to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

Bodying Agents and Thickeners

Suitable bodying agents are primarily fatty alcohols or hydroxy fattyalcohols having 12 to 22, and preferably 16 to 18, carbon atoms, andalso partial glycerides, fatty acids or hydroxy fatty acids. Preferenceis given to a combination of these substances with alkyl oligoglucosidesand/or fatty acid N-methylglucamides of identical chain length and/orpolyglycerol poly-12-hydroxystearates. Suitable thickeners are, forexample, Aerosil grades (hydrophilic silicas), polysaccharides, inparticular xanthan gum, guar guar, agar agar, alginates and Tyloses,carboxymethylcellulose, hydroxyethylcellulose andhydroxypropylcellulose, and also relatively high molecular weightpolyethylene glycol mono- and diesters of fatty acids, polyacrylates(e.g. Carbopols® and Pemulen grades from Goodrich; Synthalens® fromSigma; Keltrol grades from Kelco; Sepigel grades from Seppic; Salcaregrades from Allied Colloids), polyacrylamides, polymers, polyvinylalcohol and polyvinylpyrrolidone. Bentonites, such as, for example,Bentone® Gel VS 5PC (Rheox), which is a mixture of cyclopentasiloxane,disteardimonium hectorite and propylene carbonate, have also proven tobe particularly effective. Also suitable are surfactants, such as, forexample, ethoxylated fatty acid glycerides, esters of fatty acids withpolyols such as, for example, pentaerythritol or trimethylolpropane,fatty alcohol ethoxylates having a narrowed homolog distribution oralkyl oligoglucosides, and electrolytes such as sodium chloride andammonium chloride.

Superfatting Agents

Superfatting agents which can be used are substances such as, forexample, lanolin and lecithin, and polyethoxylated or acylated lanolinand lecithin derivatives, polyol fatty acid esters, monoglycerides andfatty acid alkanolamides, the latter also serving as foam stabilizers.

Stabilizers

Stabilizers which can be used are metal salts of fatty acids, such as,for example, magnesium, aluminum and/or zinc stearate or ricinoleate.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives, such as, for example, a quaternized hydroxyethylcelluloseobtainable under the name Polymer JR 400® from Amerchol, cationicstarch, copolymers of diallylammonium salts and acrylamides, quaternizedvinylpyrrolidone-vinylimidazole polymers, such as, for example,Luviquat® (BASF), condensation products of polyglycols and amines,quaternized collagen polypeptides, such as, for example, lauryldimoniumhydroxypropyl hydrolyzed collagen (Lamequat® L/Grünau), quaternizedwheat polypeptides, polyethyleneimine, cationic silicone polymers, suchas, for example, amodimethicones, copolymers of adipic acid anddimethylaminohydroxypropyldiethylenetriamine (Cartaretins®/Sandoz),copolymers of acrylic acid with dimethyldiallylammonium chloride(Merquat® 550/Chemviron), polyaminopolyamides, as described, forexample, in FR 2252840 A, and crosslinked water-soluble polymersthereof, cationic chitin derivatives, such as, for example, quaternizedchitosan, optionally in micro-crystalline dispersion, condensationproducts from dihaloalkyls, such as, for example, dibromobutane withbisdialkylamines, such as, for example, bis-dimethylamino-1,3-propane,cationic guar gum, such as, for example, Jaguar® CBS, Jaguar® C-17,Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as,for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate-crotonic acid copolymers,vinylpyrrolidone-vinyl acrylate copolymers, vinyl acetate-butylmaleate-isobornyl acrylate copolymers, methyl vinyl ether-maleicanhydride copolymers and esters thereof, uncrosslinked polyacrylic acidsand polyacrylic acids crosslinked with polyols,acrylamidopropyltrimethylammonium chloride-acrylate copolymers,octylacrylamide-methyl methacrylate-tert-butylaminoethylmethacrylate-2-hydroxypropyl methacrylate copolymers,polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers,vinylpyrrolidone-dimethylaminoethyl methacrylate-vinylcaprolactamterpolymers, and optionally derivatized cellulose ethers and silicones.Further suitable polymers and thickeners are listed in Cosm. Toil. 108,95 (1993).

Silicone Compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes,methylphenylpolysiloxanes, cyclic silicones, and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds, which can either be liquid or inresin form at room temperature. Also suitable are simethicones, whichare mixtures of dimethicones having an average chain length of from 200to 300 dimethylsiloxane units and hydrogenated silicates. A detailedreview of suitable volatile silicones can additionally be found in Toddet al., Cosm. Toil. 91, 27 (1976).

UV Light Protection Filters and Antioxidants

UV light protection factors are, for example, to be understood asmeaning organic substances (light protection filters) which are liquidor crystalline at room temperature and which are able to absorbultraviolet rays and give off the absorbed energy again in the form oflonger-wavelength radiation, e.g. heat. UVB filters can be oil-solubleor water-soluble. Examples of oil-soluble substances are:

-   -   3-benzylidenecamphor or 3-benzylidenenorcamphor and derivatives        thereof, e.g. 3-(4-methylbenzylidene)camphor, as described in EP        0693471 B1;    -   4-aminobenzoic acid derivatives, preferably 2-ethylhexyl        4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and        amyl 4-(dimethylamino)benzoate;    -   esters of cinnamic acid, preferably 2-ethylhexyl        4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl        4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate        (octocrylene);    -   esters of salicylic acid, preferably 2-ethylhexyl salicylate,        4-isopropylbenzyl salicylate, homomethyl salicylate;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy-4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone;    -   esters of benzalmalonic acid, preferably di-2-ethylhexyl        4-methoxybenzmalonate;    -   triazine derivatives, such as, for example,        2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine        and octyltriazone, as described in EP 0818450 A1 or        dioctylbutamidotriazone (Uvasorb® HEB);    -   propane-1,3-diones, such as, for example,        1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione;    -   ketotricyclo(5.2.1.0)decane derivatives, as described in EP        0694521 B1.

Suitable water-soluble substances are:

-   -   2-phenylbenzimidazole-5-sulfonic acid and the alkali metal,        alkaline earth metal, ammonium, alkylammonium, alkanolammonium        and glucammonium salts thereof;    -   sulfonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;    -   sulfonic acid derivatives of 3-benzylidenecamphor, such as, for        example, 4-(2-oxo-3-bornylidenemethyl)benzenesulfonic acid and        2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid and salts thereof.

Suitable typical UV-A filters are, in particular, derivatives ofbenzoylmethane, such as, for example,1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione,4-tert-butyl-4′-methoxydibenzoylmethane (Parsol® 1789),1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione, and enamine compounds,as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can ofcourse also be used in mixtures. Particularly favorable compositionsconsist of the derivatives of benzoylmethane e.g.4-tert-butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and 2-ethylhexyl2-cyano-3,3-phenylcinnamate (octocrylene) in combination with esters ofcinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate and/or propyl4-methoxycinnamate and/or isoamyl 4-methoxycinnamate. Advantageously,such combinations are combined with water-soluble filters such as, forexample, 2-phenylbenzimidazole-5-sulfonic acid and their alkali metal,alkaline earth metal, ammonium, alkylammonium, alkanolammonium andglucammonium salts.

As well as said soluble substances, insoluble light protection pigments,namely finely dispersed metal oxides or salts, are also suitable forthis purpose. Examples of suitable metal oxides are, in particular, zincoxide and titanium dioxide and also oxides of iron, zirconium, silicon,manganese, aluminum and cerium, and mixtures thereof. Salts which may beused are silicates (talc), barium sulfate or zinc stearate. The oxidesand salts are used in the form of the pigments for skincare andskin-protective emulsions and decorative cosmetics. The particles hereshould have an average diameter of less than 100 nm, preferably between5 and 50 nm and in particular between 15 and 30 nm. They can have aspherical shape, but it is also possible to use particles which have anellipsoidal shape or a shape deviating in some other way from thespherical form. The pigments can also be surface-treated, i.e.hydrophilicized or hydrophobicized. Typical examples are coated titaniumdioxides, such as, for example, titanium dioxide T 805 (Degussa) orEusolex® T2000 (Merck). Suitable hydrophobic coating agents are hereprimarily silicones and, specifically in this case,trialkoxyoctylsilanes or simethicones. In sunscreens, preference isgiven to using so-called micro- or nanopigments. Preference is given tousing micronized zinc oxide. Further suitable UV light protectionfilters are given in the review by P. Finkel in SÖFW-Journal 122, 543(1996) and Parf. Kosm. 3, 11 (1999).

As well as the two abovementioned groups of primary light protectionsubstances, it is also possible to use secondary light protection agentsof the antioxidant type; these interrupt the photochemical reactionchain which is triggered when UV radiation penetrates the skin. Typicalexamples thereof are amino acids (e.g. glycine, histidine, tyrosine,tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) andderivatives thereof, peptides, such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotenoids,carotenes (e.g. α-carotene, β-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl,cholesteryl and glyceryl esters thereof) and salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts), and sulfoximine compounds (e.g. buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-,hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g. pmolto μmol/kg), and also (metal) chelating agents (e.g. α-hydroxy fattyacids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g.citric acid, lactic acid, malic acid), humic acid, bile acid, bileextracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E acetate), vitaminA and derivatives (vitamin A palmitate), and coniferyl benzoate of gumbenzoin, rutic acid and derivatives thereof, α-glycosylrutin, ferulicacid, furfurylideneglucitol, carnosine, butylhydroxytoluene,butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid,trihydroxybutyrophenone, uric acid and derivatives thereof, mannose andderivatives thereof, superoxide dismutase, zinc and derivatives thereof(e.g. ZnO, ZnSO₄) selenium and derivatives thereof (e.g.selenomethionine), stilbenes and derivatives thereof (e.g. stilbeneoxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids) of said activeingredients which are suitable according to the invention.

Biogenic Active Ingredients

Biogenic active ingredients are understood as meaning, for example,tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,(deoxy)ribonucleic acid and fragmentation products thereof, β-glucans,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts, suchas, for example, prunus extract, bambara nut extract and vitamincomplexes.

Deodorants and Antimicrobial Agents

Cosmetic deodorants counteract, mask or remove body odors. Body odorsarise as a result of the effect of skin bacteria on apocrineperspiration, with the formation of degradation products which have anunpleasant odor. Accordingly, deodorants comprise active ingredientswhich act as antimicrobial agents, enzyme inhibitors, odor absorbers orodor masking agents.

Antimicrobial Agents

Suitable antimicrobial agents are, in principle, all substanceseffective against gram-positive bacteria, such as, for example,4-hydroxybenzoic acid and its salts and esters,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea,2,4,4′-trichloro-2′-hydroxydiphenyl ether (triclosan),4-chloro-3,5-dimethylphenol, 2,2′-methylenebis(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialfragrances, thymol, thyme oil, eugenol, oil of cloves, menthol, mintoil, farnesol, phenoxyethanol, glycerol monocaprate, glycerolmonocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC),salicylic acid N-alkylamides, such as, for example, n-octylsalicylamideor n-decylsalicylamide.

Enzyme Inhibitors

Suitable enzyme inhibitors are, for example, esterase inhibitors. Theseare preferably trialkyl citrates, such as trimethyl citrate, tripropylcitrate, triisopropyl citrate, tributyl citrate and, in particular,triethyl citrate (Hydagen® CAT). The substances inhibit enzyme activity,thereby reducing the formation of odor. Other substances which aresuitable esterase inhibitors are sterol sulfates or phosphates, such as,for example, lanosterol, cholesterol, campesterol, stigmasterol andsitosterol sulfate or phosphate, dicarboxylic acids and esters thereof,such as, for example, glutaric acid, monoethyl glutarate, diethylglutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acidand diethyl malonate, hydroxycarboxylic acids and esters thereof, suchas, for example, citric acid, malic acid, tartaric acid or diethyltartrate, and zinc glycinate.

Odor Absorbers

Suitable odor absorbers are substances which are able to absorb andlargely retain odor-forming compounds. They lower the partial pressureof the individual components, thus also reducing their rate ofdiffusion. It is important that in this process perfumes must remainunimpaired. Odor absorbers are not effective against bacteria. Theycomprise, for example, as main constituent, a complex zinc salt ofricinoleic acid or specific, largely odor-neutral fragrances which areknown to the person skilled in the art as “fixatives”, such as, forexample, extracts of labdanum or styrax or certain abietic acidderivatives. The odor masking agents are fragrances or perfume oils,which, in addition to their function as odor masking agents, give thedeodorants their respective fragrance note. Perfume oils which may bementioned are, for example, mixtures of natural and syntheticfragrances. Natural fragrances are extracts from flowers, stems andleaves, fruits, fruit peels, roots, woods, herbs and grasses, needlesand branches, and resins and balsams. Also suitable are animal rawmaterials, such as, for example, civet and castoreum. Typical syntheticfragrance compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Fragrance compounds of the ester type are,for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. Theethers include, for example, benzyl ethyl ether, and the aldehydesinclude, for example, the linear alkanals having 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxycitronellal, lilial and bourgeonal, the ketones include, forexample, the ionones and methyl cedryl ketone, the alcohols includeanethole, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol, and the hydrocarbons include mainlythe terpenes and balsams. Preference is, however, given to usingmixtures of different fragrances which together produce a pleasingfragrance note. Essential oils of relatively low volatility, which aremostly used as aroma components, are also suitable as perfume oils, e.g.sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamonleaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanumoil, galbanum oil, labdanum oil and lavandin oil. Preference is given tousing bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone,cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole,hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone,geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur,iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid,geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl andfloramat alone or in mixtures.

Antiperspirants

Antiperspirants reduce the formation of perspiration by influencing theactivity of the eccrine sweat glands, thus counteracting underarmwetness and body odor. Aqueous or anhydrous formulations ofantiperspirants typically comprise the following ingredients:

-   -   astringent active ingredients,    -   oil components,    -   nonionic emulsifiers,    -   coemulsifiers,    -   bodying agents,    -   auxiliaries, such as, for example, thickeners or complexing        agents and/or    -   nonaqueous solvents, such as, for example, ethanol, propylene        glycol and/or glycerol.

Suitable astringent antiperspirant active ingredients are primarilysalts of aluminum, zirconium or of zinc. Such suitable antihydroticactive ingredients are, for example, aluminum chloride, aluminumchlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrateand complex compounds thereof, e.g. with 1,2-propylene glycol, aluminumhydroxyallantoinate, aluminum chloride tartrate, aluminum zirconiumtrichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminumzirconium pentachlorohydrate and complex compounds thereof, e.g. withamino acids, such as glycine. In addition, customary oil-soluble andwater-soluble auxiliaries may be present in antiperspirants inrelatively small amounts. Such oil-soluble auxiliaries may, for example,be:

-   -   anti-inflammatory, skin-protective or perfumed essential oils,    -   synthetic skin-protective active ingredients and/or    -   oil-soluble perfume oils.

Customary water-soluble additives are, for example, preservatives,water-soluble fragrances, pH regulators, e.g. buffer mixtures,water-soluble thickeners, e.g. water-soluble natural or syntheticpolymers, such as, for example, xanthan gum, hydroxyethylcellulose,polyvinylpyrrolidone or high molecular weight polyethylene oxides.

Film Formers

Customary film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinylpyrrolidone,vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof, and similar compounds.

Antidandruff Active Ingredients

Suitable antidandruff active ingredients are pirocton olamin(1-hydroxy-4-methyl-6-(2,4,4-trimythylpentyl)-2(1H)-pyridinonemonoethanolamine salt), Baypival® (climbazole), Ketoconazole®,(4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}piperazine,ketoconazole, elubiol, selenium disulfide, sulfur colloidal, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinole polyethoxylate,sulfur tar distillates, salicylic acid (or in combination withhexachlorophene) undexylenic acid monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein undecylenic acid condensate), zincpyrithione, aluminum pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Swelling Agents

The swelling agents for aqueous phases may be montmorillonites, claymineral substances, Pemulen, and alkyl-modified Carbopol grades(Goodrich). Other suitable polymers and swelling agents are given in thereview by R. Lochhead in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, 1,2-pentanediolor ethyl butylacetylaminopropionate.

Self-Tanning Agents and Depigmentation Agents

A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosineinhibitors, which prevent the formation of melanin and are used indepigmentation agents, are, for example, arbutin, ferulic acid, kojicacid, coumaric acid and ascorbic acid (vitamin C).

Hydrotropic Agents

To improve the flow behavior, it is also possible to use hydrotropicagents, such as, for example, ethanol, isopropyl alcohol, or polyols.Polyols which are suitable here preferably have 2 to 15 carbon atoms andat least two hydroxyl groups. The polyols can also contain furtherfunctional groups, in particular amino groups, or be modified withnitrogen. Typical examples are

-   -   glycerol;    -   alkylene glycols, such as, for example, ethylene glycol,        diethylene glycol, propylene glycol, butylene glycol, hexylene        glycol, and polyethylene glycols with an average molecular        weight of from 100 to 1 000 daltons;    -   technical-grade oligoglycerol mixtures with a degree of        self-condensation of from 1.5 to 10, such as, for example,        technical-grade diglycerol mixtures with a diglycerol content of        from 40 to 50% by weight;    -   methyol compounds, such as, in particular, trimethylolethane,        trimethylolpropane, trimethylolbutane, pentaerythritol and        dipentaerythritol;    -   lower alkyl glucosides, in particular those having 1 to 8 carbon        atoms in the alkyl radical, such as, for example, methyl and        butyl glucoside;    -   sugar alcohols having 5 to 12 carbon atoms, such as, for        example, sorbitol or mannitol,    -   sugars having 5 to 12 carbon atoms, such as, for example glucose        or sucrose;    -   amino sugars, such as, for example, glucamine;    -   dialcohol amines, such as diethanolamine or        2-amino-1,3-propanediol.

Preservatives

Suitable preservatives are, for example, phenoxy ethanol, formaldehydesolution, parabenes, pentanediol or sorbic acid, and the silvercomplexes known under the name Surfacins®, and also the other classes ofsubstance listed in Annex 6, Part A and B of the Cosmetics Directive.

Perfume Oils and Aromas

Perfume oils which may be mentioned are mixtures of natural andsynthetic fragrances. Natural fragrances are extracts from flowers(lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves(geranium, patchouli, petitgrain), fruits (aniseed, coriander, cumin,juniper), fruit peels (bergamot, lemon, orange), roots (mace, angelica,celery, cardamon, costus, iris, calmus), woods (pinewood, sandalwood,guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon,lemongrass, sage, thyme), needles and branches (spruce, fir, pine,dwarf-pine), resins and balsams (galbanum, elemi, benzoin, myrrh,olibanum, opoponax). Also suitable are animal raw materials, such as,for example, civet and castoreum. Typical synthetic fragrance compoundsare products of the ester, ether, aldehyde, ketone, alcohol andhydrocarbon type. Fragrance compounds of the ester type are, forexample, benzyl acetate, phenoxyethyl isobutyrate,p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate,ethylmethylphenyl glycinate, allyl cyclohexylpropionate, styrallylpropionate and benzyl salicylate. The ethers include, for example,benzyl ethyl ether, the aldehydes include, for example, the linearalkanals having 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal, and the ketones include, for example, theionones, α-isomethylionone and methyl cedryl ketone, the alcoholsinclude anethole, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol, and the hydrocarbons include mainlythe terpenes and balsams. Preference is, however, given to usingmixtures of different fragrances which together produce a pleasingfragrance note. Essential oils of relatively low volatility, which aremostly used as aroma components, are also suitable as perfume oils, e.g.sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamonleaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanumoil, galbanum oil, labolanum oil and lavandin oil. Preference is givento using bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone,cyclamen aldehyde, linalool, boisambrene torte, ambroxan, indole,hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone,geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur,iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid,geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl andfloramat alone or in mixtures.

Suitable aromas are, for example, peppermint oil, spearmint oil, aniseoil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil,wintergreen oil, oil of cloves, menthol and the like.

Dyes

Dyes which can be used are the substances which are approved andsuitable for cosmetic purposes, as are summarized, for example, in thepublication “Kosmetische Fäirbemittel” [Cosmetic Colorants] from theFarbstoff-kommission der Deutechen Forschungsgemeinschaft [DyesCommission of the German Research Council], Verlag Chemie, Weinheim,1984, pp. 81-106. Examples are cochineal red A (C.I.16255), patent blueV (C.I.42051), indigotin (C.I.73015), chlorophyllin (C.I.75810),quinoline yellow (C.I.47005), titanium dioxide (C.I.77891), indanthreneblue RS (C.I.69800) and madder lake (C.I.58000). As a luminescent dye,it is also possible for luminol to be present. These dyes arecustomarily used in concentrations of from 0.001 to 0.1% by weight,based on the total mixture.

The total amount of auxiliaries and additives can be 1 to 50% by weight,preferably 5 to 40% by weight, based on the compositions. Thecompositions can be prepared by customary cold or hot processes;preference is given to using the phase-inversion temperature method.

Laundry Detergents, Dishwashing Detergents, Cleaners and Hand Modifiers

The surface-active compositions can, for example, also represent laundrydetergents, dishwashing detergents, cleaners or hand modifiers which canfurther comprise auxiliaries and additives typical of thesepreparations. These include, for example, anionic, nonionic, cationic,amphoteric or zwitterionic surfactants, builders, cobuilders, oil- andgrease-dissolving substances, bleaches, bleach activators,antiredeposition agents, enzymes, enzyme stabilizers, opticalbrighteners, polymers, defoamers, disintegrants, fragrances, inorganicsalts and the like, as are explained in more detail below.

Anionic Surfactants

Typical examples of anionic surfactants are soaps,alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ethersulfonates, glycerol ether sulfonates, α-methyl ester sulfonates,sulfo-fatty acids, alkyl sulfates, fatty alcohol ether sulfates,glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride(ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkyl sulfosuccinamates,sulfotriglycerides, amide soaps, ether carboxylic acids and saltsthereof, fatty acid isethionates, fatty acid sarcosinates, fatty acidtaurides, N-acylamino acids, such as, for example, acyl lactylates, acyltartrates, acyl glutamates and acyl aspartates, alkyl oligoglucosidesulfates, protein fatty acid condensates (in particular wheat-basedvegetable products) and alkyl (ether) phosphates. If the anionicsurfactants contain polyglycol ether chains, these can have aconventional homolog distribution, but preferably have a narrowedhomolog distribution. Preference is given to usingalkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates,olefinsulfonates, methyl ester sulfonates, and mixtures thereof. Typicalexamples of nonionic surfactants are fatty alcohol polyglycol ethers,alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acidamide polyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers or mixed formals, alk(en)yl oligoglycosides,fatty acid N-alkylglucamides, protein hydrolysates (in particularwheat-based vegetable products), polyol fatty acid esters, sugar esters,sorbitan esters, polysorbates and amine oxides. If the nonionicsurfactants contain polyglycol ether chains, these can have aconventional homolog distribution, but preferably have a narrowedhomolog distribution. Preference is given to using fatty alcoholpolyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyloligoglucosides.

Builders

The laundry detergents, dishwashing detergents, cleaners and handmodifiers according to the invention can further comprise additionalinorganic and organic builder substances, for example in amounts of from10 to 50% by weight and preferably 15 to 35% by weight, based on thecompositions, where the inorganic builder substances used are primarilyzeolites, crystalline phyllosilicates, amorphous silicates and, wherepermissible, also phosphates, such as, for example, tripolyphosphate.The amount of cobuilder here is to be included in the preferred amountsof phosphates.

The finely crystalline, synthetic and bonded water-containing zeoliteoften used as detergent builder is preferably zeolite A and/or P. Aszeolite P, particular preference is given, for example, to zeolite MAP®(commercial product from Crosfield). Also suitable, however, are zeoliteX and mixtures of A, X and/or P and also Y. Of particular interest isalso a cocrystallized sodium/potassium-aluminum silicate of zeolite Aand zeolite X, which is available commercially as VEGOBOND AX®(commercial product from Condea Augusta S.p.A.). The zeolite can be usedas a spray-dried powder or else as an undried stabilized suspensionstill moist from its preparation. In cases where the zeolite is used assuspension, the latter can comprise small additions of nonionicsurfactants as stabilizers, for example 1 to 3% by weight, based onzeolite, of ethoxylated C₁₂-C₁₈-fatty alcohols having 2 to 5 ethyleneoxide groups, C₁₂-C₁₄-fatty alcohols having 4 to 5 ethylene oxide groupsor ethoxylated isotridecanols. Suitable zeolites have an averageparticle size of less than 10 μm (volume distribution; measurementmethod: Coulter counter) and preferably comprise 18 to 22% by weight, inparticular 20 to 22% by weight, of bonded water.

Suitable substitutes or partial substitutes for phosphates and zeolitesare crystalline, layered sodium silicates of the general formulaNaMSi_(x)O_(2x+1).yH₂O, where M is sodium or hydrogen, x is a numberfrom 1.9 to 4 and y is a number from 0 to 20 and preferred values for xare 2, 3 or 4. Such crystalline phyllosilicates are described, forexample, in European patent application EP 0164514 A1. Preferredcrystalline phyllosilicates of the given formula are those in which M issodium and x assumes the values 2 or 3. Particular preference is givento both β- and also δ-sodium disilicates Na₂Si₂O₅.yH₂O, where β-sodiumdisilicate can be obtained, for example, by the process described ininternational patent application WO 91/08171. Further suitablephyllosilicates are known, for example, from the patent applications DE2334899 A1, EP 0026529 A1 and DE 3526405 A1. Their usability is notlimited to a specific composition or structural formula. Preference isgiven here, however, to smectites, in particular bentonites. Suitablephyllosilicates which belong to the group of water-swellable smectitesare, for example, those of the general formulae

(OH)₄Si_(8-y)Al_(y)(Mg_(x)Al_(4-x))O₂₀ montmorillonite

(OH)₄Si_(8-y)Al_(y)(Mg_(6-z)Li_(z))O₂₀ hectorite

(OH)₄Si_(8-y)Al_(y)(Mg_(6-z)Al_(z))O₂₀ saponite

where x=0 to 4, y=0 to 2, z=0 to 6. In addition, small amounts of ironcan be incorporated into the crystal lattice of the phyllosilicatesaccording to the above formulae. In addition, the phyllosilicates cancomprise hydrogen, alkali metal and alkaline earth metal ions, inparticular Na⁺ and Ca²⁺, because of their ion-exchanging properties. Theamount of water of hydration is in most cases in the range from 8 to 20%by weight and is dependent on the swelling state or on the type ofprocessing. Phyllosilicates which can be used are, for example, knownfrom U.S. Pat. No. 3,966,629, U.S. Pat. No. 4,062,647, EP 0026529 A1 andEP 0028432 A1. Preference is given to using phyllosilicates which,because of an alkali metal treatment, are largely free from calcium ionsand strongly coloring iron ions.

Preferred builder substances also include amorphous sodium silicateswith an Na₂O:SiO₂ modulus of from 1:2 to 1:3.3, preferably from 1:2 to1:2.8 and in particular from 1:2 to 1:2.6, which have delayeddissolution and secondary detergency properties. The delayed dissolutioncompared with conventional amorphous sodium silicates can be broughtabout in a variety of ways, for example by surface treatment,compounding, compaction/compression or by overdrying. For the purposesof this invention, the term “amorphous”, is also to be understood asmeaning “X-ray-amorphous”. This means that, in X-ray diffractionexperiments, the silicates do not produce sharp X-ray reflectionstypical of crystalline substances, but, at best, one or more maxima ofthe scattered X-ray radiation having a breadth of several degree unitsof the diffraction angle. However, particularly good builder propertiesmay very likely result if the silicate particles produce poorly definedor even sharp diffraction maxima in electron diffraction experiments.This is to be interpreted to the effect that the products havemicrocrystalline regions with a size from 10 to a few hundred nm,preference being given to values up to a maximum of 50 nm and inparticular up to a maximum of 20 nm. Such so-called X-ray-amorphoussilicates, which likewise have delayed dissolution compared withtraditional waterglasses, are described, for example, in the Germanpatent application DE 4400024 A1. Particular preference is given tocompressed/compacted amorphous silicates, compounded amorphous silicatesand overdried X-ray-amorphous silicates.

It is of course also possible to use the generally known phosphates asbuilder substances if such a use is not to be avoided for ecologicalreasons. Suitable are, in particular, the sodium salts of theorthophosphates, the pyrophosphates and, in particular, thetripolyphosphates. Their content is generally not more than 25% byweight, preferably not more than 20% by weight, in each case based onthe finished composition. In some cases, it has been found that, inparticular, tripolyphosphates, even in small amounts up to at most 10%by weight, based on the finished composition, in combination with otherbuilder substances lead to a synergistic improvement in the secondarydetergency.

Cobuilders

Organic framework substances which can be used and are suitable ascobuilders are, for example, the polycarboxylic acids which can be usedin the form of their sodium salts, such as citric acid, adipic acid,succinic acid, glutaric acid, tartaric acid, sugar acids,aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such a useis not objectionable for ecological reasons, and mixtures thereof.Preferred salts are the salts of the polycarboxylic acids, such ascitric acid, adipic acid, succinic acid, glutaric acid, tartaric acid,sugar acids and mixtures thereof. The acids per se can also be used. Inaddition to their builder action, the acids typically also have theproperty of an acidifying component and thus also serve for setting arelatively low and relatively mild pH of laundry detergents or cleaners.In this connection, particular mention may be made of citric acid,succinic acid, glutaric acid, adipic acid, gluconic acid and anymixtures thereof.

Further suitable organic builder substances are dextrins, for exampleoligomers or polymers of carbohydrates which can be obtained by partialhydrolysis of starches. The hydrolysis can be carried out in accordancewith customary, for example acid-catalyzed or enzyme-catalyzed,processes. The hydrolysis products preferably have average molar massesin the range from 400 to 500 000. Here, a polysaccharide with a dextroseequivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30,is preferred, where DE is a usual measure of the reducing action of apolysaccharide compared with dextrose, which has a DE of 100. It ispossible to use either maltodextrins with a DE between 3 and 20 and dryglucose syrups with a DE between 20 and 37, and also so-called yellowdextrins and white dextrins with relatively high molar masses in therange from 2 000 to 30 000. A preferred dextrin is described in Britishpatent application GB 9419091 A1. The oxidized derivatives of suchdextrins are their reaction products with oxidizing agents which areable to oxidize at least one alcohol function of the saccharide ring togive the carboxylic acid function. Such oxidized dextrins and processesfor their preparation are known, for example, from European patentapplications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496A1, and the international patent applications WO 92/18542, WO 93/08251,WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. Alsosuitable is an oxidized oligosaccharide according to German patentapplication DE 19600018 A1. A product oxidized on C₆ of the saccharidering may be particularly advantageous.

Further suitable co-builders are oxydisuccinates and other derivativesof disuccinates, preferably ethylenediamine disuccinate. Particularpreference is also given in this connection to glycerol disuccinates andglycerol trisuccinates, as are described, for example, in US-Americanpatent specifications U.S. Pat. No. 4,524,009, U.S. Pat. No. 4,639,325,in the European patent application EP 0150930 A1 and the Japanese patentapplication JP 93/339896. Suitable use amounts in zeolite-containingand/or silicate-containing formulations are 3 to 15% by weight. Furtherorganic co-builders which can be used are, for example, acetylatedhydroxycarboxylic acids or salts thereof, which may optionally also bein lactone form and which contain at least 4 carbon atoms and at leastone hydroxyl group and a maximum of two acid groups. Such co-buildersare described, for example, in international patent application WO95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium saltsof polyacrylic acid or of polymethacrylic acid, for example those with arelative molecular mass of from 800 to 150 000 (based on acid and ineach case measured against polystyrenesulfonic acid). Suitablecopolymeric polycarboxylates are, in particular, those of acrylic acidwith methacrylic acid and of acrylic acid or methacrylic acid withmaleic acid. Copolymers of acrylic acid with maleic acid which contain50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleicacid have proven particularly suitable. Their relative molecular mass,based on free acids, is generally 5 000 to 200 000, preferably 10 000 to120 000 and in particular 50 000 to 100 000 (in each case measuredagainst polystyrenesulfonic acid). The (co)polymeric polycarboxylatescan either be used as powder or as aqueous solution, preference beinggiven to 20 to 55% by weight strength aqueous solutions. Granularpolymers are in most cases added subsequently to one or more basegranulates. Particular preference is also given to biodegradablepolymers of more than two different monomer units, for example thosewhich, according to DE 4300772 A1, contain salts of acrylic acid and ofmaleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers,or, according to DE 4221381 C2, salts of acrylic acid and of2-alkylallylsulfonic acid and sugar derivatives as monomers. Furtherpreferred copolymers are those which are described in German patentapplications DE 4303320 A1 and DE 4417734 A1 and have, as monomers,preferably acrolein and acrylic acid/acrylic acid salts or acrolein andvinyl acetate. Further preferred builder substances are also polymericaminodicarboxylic acids, salts thereof or precursor substances thereof.Particular preference is given to polyaspartic acids or salts andderivatives thereof.

Further suitable builder substances are polyacetals, which can beobtained by reacting dialdehydes with polyolcarboxylic acids which have5 to 7 carbon atoms and at least 3 hydroxyl groups, for example asdescribed in European patent application EP 0280223 A1. Preferredpolyacetals are obtained from dialdehydes such as glyoxal,glutaraldehyde, terephthalaldehyde and mixtures thereof and frompolyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.

Oil- and Grease-Dissolving Substances

In addition, the compositions can also comprise components which have apositive effect on the ability to wash oil and grease out of textiles.Preferred oil- and grease-dissolving components include, for example,nonionic cellulose ethers, such as methylcellulose andmethylhydroxypropylcellulose having a proportion of methoxy groups offrom 15 to 30% by weight and of hydroxypropoxy groups of from 1 to 15%by weight, in each case based on the nonionic cellulose ethers, and thepolymers, known from the prior art, of phthalic acid and/or ofterephthalic acid, or of derivatives thereof, in particular polymers ofethylene terephthalates and/or polyethylene glycol terephthalates oranionically and/or nonionically modified derivatives thereof. Of these,particular preference is given to the sulfonated derivatives of phthalicacid polymers and of terephthalic acid polymers.

Bleaches and Bleach Activators

Among the compounds which supply H₂O₂ in water and which serve asbleaches, sodium perborate tetrahydrate and sodium perborate monohydrateare of particular importance. Further bleaches which can be used are,for example, sodium percarbonate, peroxypyrophosphates, citrateperhydrates, and H₂O₂-supplying peracidic salts or peracids, such asperbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracidor diperdodecanedioic acid. The content of bleaches in the compositionsis preferably 5 to 35% by weight and in particular up to 30% by weight,where perborate monohydrate or percarbonate is used advantageously.

Bleach activators which can be used are compounds which, underperhydrolysis conditions, produce aliphatic peroxocarboxylic acidshaving, preferably, 1 to 10 carbon atoms, in particular 2 to 4 carbonatoms, and/or optionally substituted perbenzoic acid. Substances whichcarry O- and/or N-acyl groups of said number of carbon atoms and/oroptionally substituted benzoyl groups are suitable. Preference is givento polyacylated alkylenediamines, in particulartetraacetylethylenediamine (TAED), acylated triazine derivatives, inparticular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycolurils, in particular tetraacetylglycoluril (TAGU),N-acylimides, in particular N-nonanoylsuccinimide (NOST), acylatedphenolsulfonates, in particular n-nonanoyl- orisononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,in particular phthalic anhydride, acylated polyhydric alcohols, inparticular triacetin, ethylene glycol diacetate,2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from Germanpatent applications DE 19616693 A1 and DE 19616767 A1, and acetylatedsorbitol and mannitol or mixtures thereof described in European patentapplication EP 0525239 A1 (SORMAN), acylated sugar derivatives, inparticular pentaacetylglucose (PAG), pentaacetylfructose,tetraacetylxylose and octaacetyllactose, and acetylated, optionallyN-alkylated glucamine and gluconolactone, and/or N-acylated lactams, forexample N-benzoylcaprolactam, which are known from international patentapplications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO95/14759 and WO 95/17498. The hydrophilically substituted acylacetalsknown from German patent application DE 19616769 A1, and the acyllactamsdescribed in German patent application DE 196 16 770 and internationalpatent application WO 95/14075 are likewise used with preference. Thecombinations of conventional bleach activators known from German patentapplication DE 4443177 A1 can also be used. Such bleach activators arepresent in the customary quantitative range, preferably in amounts offrom 1% by weight to 10% by weight, in particular 2% by weight to 8% byweight, based on the overall composition. In addition to theabove-listed conventional bleach activators, or instead of them, thesulfonimines known from European patent specifications EP 0446982 B1 andEP 0453 003 B1 and/or bleach-boosting transition metal salts ortransition metal complexes may also be present as so-called bleachcatalysts. Suitable transition metal compounds include, in particular,the manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexesknown from German patent application DE 19529905 A1, and theirN-analogous compounds known from German patent application DE 19620267A1, the manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonylcomplexes known from German patent application DE 19536082 A1, themanganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium andcopper complexes having nitrogen-containing tripod ligands described inGerman patent application DE 19605688 A1, the cobalt-, iron-, copper-and ruthenium-amine complexes known from German patent application DE19620411 A1, the manganese, copper and cobalt complexes described inGerman patent application DE 4416438 A1, the cobalt complexes describedin European patent application EP 0272030 A1, the manganese complexesknown from European patent application EP 0693550 A1, the manganese,iron, cobalt and copper complexes known from European patentspecification EP 0392592 A1, and/or the manganese complexes described inEuropean patent specification EP 0443651 B1 or European patentapplications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1,EP 0544490 A1 and EP 0544519 A1. Combinations of bleach activators andtransition metal bleach catalysts are known, for example, from Germanpatent application DE 19613103 A1 and international patent applicationWO 95/27775. Bleach-boosting transition metal complexes, in particularwith the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, are used incustomary amounts, preferably in an amount up to 1% by weight, inparticular from 0.0025% by weight to 0.25% by weight and particularlypreferably from 0.01% by weight to 0.1% by weight, in each case based onthe overall composition.

Enzymes and Enzyme Stabilizers

Suitable enzymes are, in particular, those from the class of hydrolases,such as proteases, esterases, lipases or lipolytic enzymes, amylases,cellulases or other glycosylhydrolases and mixtures of said enzymes. Allof these hydrolases contribute during washing to the removal of stains,such as protein, grease or starchy stains, and redeposition. Cellulasesand other glycosyl hydrolases may, by removing pilling and microfibrils,contribute to color retention and to an increase in the softness of thetextile. For bleaching or for inhibiting color transfer, it is alsopossible to use oxidoreductases. Particularly suitable enzymatic activeingredients are those obtained from bacterial strains or fungi, such asBacillus subtilis, Bacillus licheniformis, Streptomyces griseus andHumicola insolens. Preference is given to using proteases of thesubtilisin type and, in particular, proteases obtained from Bacilluslentus. Of particular interest in this connection are enzyme mixtures,for example mixtures of protease and amylase or protease and lipase orlipolytic enzymes, or protease and cellulase or of cellulase and lipaseor lipolytic enzymes or of protease, amylase and lipase or lipolyticenzymes or protease, lipase or lipolytic enzymes and cellulase, inparticular, however, protease- and/or lipase-containing mixtures ormixtures containing lipolytic enzymes. Examples of such lipolyticenzymes are the known cutinases. Peroxidases or oxidases have alsoproven suitable in some cases. Suitable amylases include, in particular,α-amylases, isoamylases, pullulanases and pectinases. The cellulasesused are preferably cellobiohydrolases, endoglucanases andβ-glucosidases, which are also called cellobiases, or mixtures thereof,Since the various cellulase types differ in their CMCase and avicelaseactivities, it is possible to adjust the desired activities throughtargeted mixing of the cellulases.

The enzymes for their part can also be adsorbed on carrier substancesand/or embedded in coating substances in order to protect them againstpremature decomposition. The proportion of enzymes, enzyme mixtures orenzyme granulates can, for example, be from about 0.1 to 5% by weight,preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the compositionscan comprise further enzyme stabilizers. For example, 0.5 to 1% byweight of sodium formate can be used. The use of proteases which havebeen stabilized with soluble calcium salts and a calcium content of,preferably, about 1.2% by weight, based on the enzyme, is also possible.Apart from calcium salts, magnesium salts also serve as stabilizers.However, the use of boron compounds, for example of boric acid, boronoxide, borax and other alkali metal borates, such as the salts oforthoboric acid (H₃BO₃), of metaboric acid (HBO₂) and of pyroboric acid(tetraboric acid H₂B₄O₇) is particularly advantageous.

Antiredeposition Agents

Antiredeposition agents have the task of keeping the soil detached fromthe fiber in suspended form in the liquor, and thus preventingreattachment of the soil. For this purpose, water-soluble colloids of amostly organic nature are suitable, for example the water-soluble saltsof polymeric carboxylic acids, glue, gelatin, salts of ether carboxylicacids or ether sulfonic acids of starch or of cellulose or salts ofacidic sulfuric esters of cellulose or of starch. Water-solublepolyamides which contain acidic groups are also suitable for thispurpose. In addition, it is also possible to use soluble starchpreparations, and starch products other than those mentioned above, e.g.degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also beused. Preference is, however, given to using cellulose ethers, such ascarboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcelluloseand mixed ethers, such as methylhydroxyethylcellulose,methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixturesthereof, and polyvinylpyrrolidone, for example in amounts of from 0.1 to5% by weight, based on the compositions.

Optical Brighteners

The compositions can comprise derivatives of diaminostilbenedisulfonicacid, or alkali metal salts thereof, as optical brighteners. Forexample, salts of4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonic acid or compounds constructed in a similar waywhich carry a diethanolamino group, a methylamino group, an anilinogroup or a 2-methoxyethylamino group instead of the morpholino group aresuitable. Brighteners of the substituted diphenylstyryl type may also bepresent, e.g. the alkali metal salts of 4,4′-bis(2-sulfostyryl)diphenyl,4,4′-bis(4-chloro-3-sulfostyryl)-diphenyl, or4-(4-chlorostyryl)-4′-(2-sulfostyryl)diphenyl. Mixtures of theabove-mentioned brighteners may also be used. Uniformly white granulatesare obtained if the compositions comprise, in addition to the customarybrighteners in customary amounts, for example between 0.1 and 0.5% byweight, preferably between 0.1 and 0.3% by weight, also small amounts,for example 10⁻⁶ to 10⁻³% by weight, preferably around 10⁻⁵% by weight,of a blue dye. A particularly preferred dye is Tinolux® (commercialproduct from Ciba-Geigy).

Polymers

Suitable soil-repellent polymers are those which preferably containethylene terephthalate and/or polyethylene glycol terephthalate groups,where the molar ratio of ethylene terephthalate to polyethylene glycolterephthalate may be in the range from 50:50 to 90:10. The molecularweight of the linking polyethylene glycol units is, in particular, inthe range from 750 to 5000, i.e. the degree of ethoxylation of thepolyethylene glycol group-containing polymers may be about 15 to 100.The polymers are characterized by an average molecular weight of about5000 to 200 000 and can have a block structure, but preferably have arandom structure. Preferred polymers are those with ethyleneterephthalate/polyethylene glycol terephthalate molar ratios of fromabout 65:35 to about 90:10, preferably from about 70:30 to 80:20. Alsopreferred are those polymers which have linking polyethylene glycolunits with a molecular weight of from 750 to 5 000, preferably from 1000 to about 3 000 and a molecular weight of the polymer from about 10000 to about 50 000. Examples of commercially available polymers are theproducts Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Defoamers

Defoamers which can be used are wax-like compounds. “Wax-like” is to beunderstood as meaning those compounds which have a melting point atatmospheric pressure above 25° C. (room temperature), preferably above50° C. and in particular above 70° C. The wax-like defoamer substancesare virtually insoluble in water, i.e. at 20° C. they have a solubilitybelow 0.1 by weight in 100 g of water. In principle, all wax-likedefoamer substances known from the prior art may be present. Suitablewax-like compounds are, for example, bisamides, fatty alcohols, fattyacids, carboxylic esters of mono- and polyhydric alcohols, and paraffinwaxes or mixtures thereof. Alternatively, the silicone compounds knownfor this purpose can of course also be used.

Suitable paraffin waxes are generally a complex mixture of substanceswithout a sharp melting point. For characterization, its melting rangeis usually determined by differential thermoanalysis (DTA), as describedin “The Analyst,” 87 (1962), 420, and/or its solidification point. Thisis to be understood as meaning the temperature at which the paraffinconverts from the liquid state to the solid state by slow cooling. Here,paraffins which are entirely liquid at room temperature, i.e. those witha solidification point below 25° C., cannot be used according to theinvention. The soft waxes, which have a melting point in the range from35 to 50° C. preferably include the group of petrolatums andhydrogenation products thereof. They are composed of microcrystallineparaffins and up to 70% by weight of oil, have an ointment-like toplastically solid consistency and represent bitumen-free residues frompetroleum refining. Particular preference is given to distillationresidues (petrolatum stock) of certain paraffin-base and mixed-basecrude oils which are further processed to give vaseline. Preferably,they are also bitumen-free, oil-like to solid hydrocarbons depositedfrom distillation residues of paraffin-base and mixed-base crude oilsand cylinder oil distillates by means of solvents. They are ofsemisolid, viscous, tacky or plastically solid consistency and havemelting points between 50 and 70° C. These petrolatums represent themost important starting base for the preparation of microcrystallinewaxes. Also suitable are the solid hydrocarbons having melting pointsbetween 63 and 79° C. deposited from high-viscosity, paraffin-containinglubricating oil distillates during deparaffinization. These petrolatumsare mixtures of microcrystalline waxes and high-melting n-paraffins. Itis possible to use, for example, the paraffin wax mixtures known from EP0309931 A1 which are composed of, for example, 26% by weight to 49% byweight of microcrystalline paraffin wax with a solidification point of62° C. to 90° C., 20% by weight to 49% by weight of hard paraffin with asolidification point of 42° C. to 56° C. and 2% by weight to 25% byweight of soft paraffin with a solidification point of from 35° C. to40° C. Preference is given to using paraffins or paraffin mixtures whichsolidify in the range from 30° C. to 90° C. In this connection, it is tobe taken into consideration that even paraffin wax mixtures which appearto be solid at room temperature may also comprise varying proportions ofliquid paraffin. In the case of the paraffin waxes which can be usedaccording to the invention, this liquid proportion is as low as possibleand is preferably not present at all. Thus, particularly preferredparaffin wax mixtures have at 30° C. a liquid content of less than 10%by weight, in particular of from 2% by weight to 5% by weight, at 40° C.a liquid content of less than 30% by weight, preferably of from 5% byweight to 25% by weight and in particular from 5% by weight to 15% byweight, at 60° C. a liquid content of from 30% by weight to 60% byweight, in particular from 40% by weight to 55% by weight, at 80° C. aliquid content of from 80% by weight to 100% by weight and at 90° C. aliquid content of 100% by weight. The temperature at which a liquidcontent of 100% by weight of the paraffin wax is achieved is, in thecase of particularly preferred paraffin wax mixtures, still below 85°C., in particular 75° C. to 82° C. The paraffin waxes may be petrolatum,microcrystalline waxes or hydrogenated or partially hydrogenatedparaffin waxes.

Suitable bisamides as defoamers are those which are derived fromsaturated fatty acids having 12 to 22, preferably 14 to 18, carbonatoms, and from alkylenediamines having 2 to 7 carbon atoms. Suitablefatty acids are lauric acid, myristic acid, stearic acid, arachidic acidand behenic acid, and mixtures thereof, as are obtainable from naturalfats or hydrogenated oils, such as tallow or hydrogenated palm oil.Suitable diamines are, for example, ethylenediamine,1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, p-phenylenediamine and tolylenediamine. Preferreddiamines are ethylenediamine and hexamethylenediamine. Particularlypreferred bisamides are bismyristoylethylenediamine,bispalmitoylethylenediamine, bis-stearoylethylenediamine and mixturesthereof, and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic esters as defoamers are derived from carboxylicacids having 12 to 28 carbon atoms. In particular, these are esters ofbehenic acid, stearic acid, hydroxystearic acid, oleic acid, palmiticacid, myristic acid and/or lauric acid. The alcohol moiety of thecarboxylic ester comprises a mono- or polyhydric alcohol having from 1to 28 carbon atoms in the hydro-carbon chain. Examples of suitablealcohols are behenyl alcohol, arachidyl alcohol, cocoyl alcohol,12-hydroxy-stearyl alcohol, oleyl alcohol and lauryl alcohol, and alsoethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol,pentaerythritol, sorbitan and/or sorbitol. Preferred esters are those ofethylene glycol, glycerol and sorbitan, where the acid moiety of theester is, in particular, chosen from behenic acid, stearic acid, oleicacid, palmitic acid or myristic acid. Suitable esters of polyhydricalcohols are, for example, xylitol monopalmitate, pentaerythritolmonostearate, glycerol monostearate, ethylene glycol monostearate andsorbitan monostearate, sorbitan palmitate, sorbitan monolaurate,sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitandioleate, and mixed tallow alkyl sorbitan monoesters and diesters.Glycerol esters which can be used are the mono-, di- or triesters ofglycerol and said carboxylic acids, preference being given to the mono-or diesters. Glycerol monostearate, glycerol monooleate, glycerolmonopalmitate, glycerol monobehenate and glycerol distearate areexamples thereof. Examples of suitable natural esters as defoamers arebeeswax, which consists primarily of the esters CH₃(CH₂)₂₄COO(CH₂)₂₇CH₃and CH₃(CH₂)₂₆COO(CH₂)₂₅CH₃, and carnauba wax, which is a mixture ofcarnaubic acid alkyl esters, often in combination with small amounts offree carnaubic acid, further long-chain acids, high molecular weightalcohols and hydrocarbons.

Suitable carboxylic acids as further defoamer compound are, inparticular, behenic acid, stearic acid, oleic acid, palmitic acid,myristic acid and lauric acid, and mixtures thereof as are obtainablefrom natural fats or optionally hydrogenated oils, such as tallow orhydrogenated palm oil. Preference is given to saturated fatty acidshaving 12 to 22, in particular 18 to 22, carbon atoms. The correspondingfatty alcohols of the same carbon chain length may likewise be used.

In addition, dialkyl ethers may additionally be present as defoamers.The ethers may have an asymmetrical or symmetrical structure, i.e.contain two identical or different alkyl chains, preferably having 8 to18 carbon atoms. Typical examples are di-n-octyl ether, di-isooctylether and di-n-stearyl ether. Dialkyl ethers which have a melting pointabove 25° C., in particular above 40° C. are particularly suitable.

Further suitable defoamer compounds are fatty ketones, which can beobtained in accordance with the relevant methods of preparative organicchemistry. They are prepared, for example, starting from carboxylic acidmagnesium salts, which are pyrolyzed at temperatures above 300° C. withelimination of carbon dioxide and water, for example in accordance withGerman laid-open specification DE 2553900 A. Suitable fatty ketones arethose which are prepared by pyrolysis of the magnesium salts of lauricacid, myristic acid, palmitic acid, palmitoleic acid, stearic acid,oleic acid, elaidic acid, petroselic acid, arachidic acid, gadoleicacid, behenic acid or erucic acid.

Further suitable defoamers are fatty acid polyethylene glycol esters,which are preferably obtained by homogeneous base-catalyzed additionreaction of ethylene oxide with fatty acids. In particular, the additionreaction of ethylene oxide with the fatty acids is carried out in thepresence of alkanolamines as catalysts. The use of alkanolamines,specifically triethanolamine, leads to an extremely selectiveethoxylation of the fatty acids, particularly when the aim is to preparecompounds which have a low degree of ethoxylation. Within the group offatty acid polyethylene glycol esters, preference is given to thosewhich have a melting point above 25° C., in particular above 40° C.

Within the group of wax-like defoamers, particular preference is givento the paraffin waxes described used alone as wax-like defoamers, or ina mixture with one of the other wax-like defoamers, where the proportionof paraffin waxes in the mixture preferably constitutes more than 50% byweight, based on wax-like defoamer mixture. The paraffin waxes can beapplied to supports as required. Suitable carrier materials are allknown inorganic and/or organic carrier materials. Examples of typicalinorganic carrier materials are alkali metal carbonates, alumosilicates,water-soluble phyllosilicates, alkali metal silicates, alkali metalsulfates, for example sodium sulfate, and alkali metal phosphates. Thealkali metal silicates are preferably a compound with an alkali metaloxide to SiO₂ molar ratio of from 1:1.5 to 1:3.5. The use of suchsilicates results in particularly good particle properties, inparticular high abrasion stability and nevertheless a high dissolutionrate in water. The aluminosilicates referred to as carrier materialinclude, in particular, the zeolites, for example zeolite NaA and NaX.The compounds referred to as water-soluble phyllosilicates include, forexample, amorphous or crystalline water glass. In addition, it ispossible to use silicates which are available commercially under thename Aerosil® or Sipernat®. Suitable organic carrier materials are, forexample, film-forming polymers, for example polyvinyl alcohols,polyvinylpyrrolidones, poly(meth)acrylates, polycarboxylates, cellulosederivatives and starch. Cellulose ethers which can be used are, inparticular, alkali metal carboxymethylcellulose, methylcellulose,ethylcellulose, hydroxyethylcellulose and so-called cellulose mixedethers, such as, for example, methylhydroxyethylcellulose andmethylhydroxypropylcellulose, and mixtures thereof. Particularlysuitable mixtures are composed of sodium carboxymethylcellulose andmethyl-cellulose, where the carboxymethylcellulose usually has a degreeof substitution of from 0.5 to 0.8 carboxymethyl groups peranhydroglucose unit and the methylcellulose has a degree of substitutionof from 1.2 to 2 methyl groups per anhydroglucose unit. The mixturespreferably comprise alkali metal carboxymethylcellulose and nonioniccellulose ethers in weight ratios of from 80:20 to 40:60, in particularfrom 75:25 to 50:50. A suitable carrier is also natural starch which iscomposed of amylose and amylopectin. Natural starch is the term used todescribe starch such as is available as an extract from natural sources,for example from rice, potatoes, corn and wheat. Natural starch is acommercially available product and thus readily available. As carriermaterials it is possible to use one or more of the compounds mentionedabove, in particular chosen from the group of alkali metal carbonates,alkali metal sulfates, alkali metal phosphates, zeolites, water-solublephyllosilicates, alkali metal silicates, polycarboxylates, celluloseethers, polyacrylate/polymethacrylate and starch. Particularly suitablemixtures are those of alkali metal carbonates, in particular sodiumcarbonate, alkali metal silicates, in particular sodium silicate, alkalimetal sulfates, in particular sodium sulfate, and zeolites.

Suitable silicones are customary organopolysiloxanes which may have acontent of finely divided silica, which in turn may also be silanized.Such organopolysiloxanes are described, for example, in European patentapplication EP 0496510 A1. Particular preference is given topolydiorganosiloxanes and, in particular, polydimethylsiloxanes whichare known from the prior art. Suitable polydiorganosiloxanes have avirtually linear chain and have a degree of oligomerization of from 40to 1 500. Examples of suitable substituents are methyl, ethyl, propyl,isobutyl, tert-butyl and phenyl. Also suitable are amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds, which may either be liquid or inresin form at room temperature. Also suitable are simethicones, whichare mixtures of dimethicones having an average chain length of from 200to 300 dimethylsiloxane units and hydrogenated silicates. As a rule, thesilicones generally, and the polydiorganosiloxanes in particular,contain finely divided silica, which may also be silanized. For thepurposes of the present invention, silica-containingdimethylpolysiloxanes are particularly suitable. Thepolydiorganosiloxanes advantageously have a Brookfield viscosity at 25°C. (spindle 1, 10 rpm) in the range from 5 000 mPas to 30 000 mPas, inparticular from 15 000 to 25 000 mPas. The silicones are preferably usedin the form of their aqueous emulsions. The silicone is generally addedto an initial charge of water with stirring. If desired, in order toincrease the viscosity of the aqueous silicone emulsions, it is possibleto add thickeners, as are known from the prior art. These may beinorganic and/or organic in nature, and particular preference is givento nonionic cellulose ethers, such as methylcellulose, ethylcelluloseand mixed ethers, such as methylhydroxyethylcellulose,methylhydroxypropylcellulose, methylhydroxybutylcellulose, and anioniccarboxycellulose grades, such as carboxymethylcellulose sodium salt(abbreviation CMC). Particularly suitable thickeners are mixtures of CMCto nonionic cellulose ethers in the weight ratio 80:20 to 40:60, inparticular 75:25 to 60:40. Usually, and particularly in the case of theaddition of the described thickener mixtures, recommended useconcentrations are from about 0.5 to 10% by weight, in particular from2.0 to 6% by weight, calculated as thickener mixture and based onaqueous silicone emulsion. The content of silicones of the typedescribed in the aqueous emulsions is advantageously in the range from 5to 50 by weight, in particular from 20 to 40% by weight, calculated assilicones and based on aqueous silicone emulsion. According to a furtheradvantageous embodiment, the aqueous silicone solutions receive, asthickener, starch accessible from natural sources, for example fromrice, potatoes, corn and wheat. The starch is advantageously present inamounts of from 0.1 up to 50% by weight, based on silicone emulsion and,in particular, in a mixture with the already described thickenermixtures of sodium carboxymethylcellulose and a nonionic cellulose etherin the amounts already given. To prepare the aqueous silicone emulsions,the procedure expediently involves allowing the optionally presentthickeners to preswell in water before adding the silicones. Thesilicones are expediently incorporated using effective stirring andmixing devices.

Disintegrants

The solid preparations can further comprise disintegrants. This term isto be understood as meaning substances which are added to the shapedbodies in order to accelerate their disintegration upon contact withwater. Overviews on this subject can be found, for example, in J. Pharm.Sci. 61 (1972), Römpp Chemilexikon, 9^(th) Edition, volume 6, p. 4440and Voigt “Lehrbuch der pharmazeutischen Technologie” [Textbook ofPharmaceutical Technology] (6^(th) Edition, 1987, pp. 182-184). Thesesubstances increase in volume upon ingress of water, with on the onehand an increase in the intrinsic volume (swelling) and on the otherhand, by way of release of gases as well, the possibility of generatinga pressure which causes the tablet to disintegrate into smallerparticles. Examples of established disintegration auxiliaries arecarbonate/citric acid systems, with the use of other organic acids alsobeing possible. Examples of swelling disintegration auxiliaries aresynthetic polymers such as optionally crosslinked polyvinylpyrrolidone(PVP) or natural polymers and/or modified natural substances such ascellulose and starch and their derivatives, alginates or caseinderivatives. Preferred disintegrants used for the purposes of thepresent invention are disintegrants based on cellulose. Pure cellulosehas the formal gross composition (C₆H₁₀O₅)_(n), and, consideredformally, is a β-1,4-polyacetal of cellobiose, which itself isconstructed from two molecules of glucose. Suitable celluloses consistof about 500 to 5 000 glucose units and, accordingly, have average molarmasses of from 50 000 to 500 000. Cellulose-based disintegrants whichcan be used for the purposes of the present invention are also cellulosederivatives obtainable by polymer-analogous reactions from cellulose.Such chemically modified celluloses include, for example, products ofesterifications and etherifications in which hydroxyl hydrogen atomshave been substituted. However, celluloses in which the hydroxyl groupshave been replaced by functional groups not attached via an oxygen atommay also be used as cellulose derivatives. The group of cellulosederivatives includes, for example, alkali metal celluloses,carboxymethylcellulose (CMC), cellulose esters and ethers and alsoaminocelluloses. Said cellulose derivatives are preferably not usedalone as cellulose-based disintegrants, but instead are used in amixture with cellulose. The cellulose derivative content of thesemixtures is preferably less than 50% by weight, particularly preferablyless than 20% by weight, based on the cellulose-based disintegrant. Aparticularly preferred cellulose-based disintegrant used is purecellulose which is free from cellulose derivatives. A furthercellulose-based disintegrant, or constituent of this component, whichmay be used is microcrystalline cellulose. This microcrystallinecellulose is obtained by partial hydrolysis of celluloses underconditions which attack only the amorphous regions (approximately 30% ofthe total cellulose mass) of the celluloses and break them upcompletely, but leave the crystalline regions (about 70%) intact.Subsequent deaggregation of the microfine celluloses resulting from thehydrolysis yields the microcrystalline celluloses, which have primaryparticle sizes of approximately 5 μm and can be compacted, for example,to give granulates having an average particle size of 200 μm. Thedisintegrants can, viewed macroscopically, be homogeneously distributedwithin the shaped body, but, viewed microscopically, form zones ofincreased concentration as a result of the preparation. Disintegrantswhich may be present for the purposes of the invention, such as, forexample, kollidon, alginic acid and alkali metal salts thereof,amorphous and also partially crystalline phyllosilicates (bentonites),polyacrylates, polyethylene glycols are given, for example, in theprinted specifications WO 98/40462 (Rettenmaier), WO 98/55583 and WO98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 A1(Henkel). Reference is expressly made to the teaching of thesespecifications. The shaped bodies can comprise the disintegrants inamounts of from 0.1 to 25% by weight, preferably 1 to 20% by weight andin particular 5 to 15% by weight, based on the shaped bodies.

Fragrances

Perfume oils or fragrances which can be used are individual fragrancecompounds, e.g. the synthetic products of the ester, ether, aldehyde,ketone, alcohol and hydrocarbon type. Fragrance compounds of the estertype are, for example, benzyl acetate, phenoxyethyl isobutyrate,p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allyl cyclohexylpropionate, styrallyl propionateand benzyl salicylate. The ethers include, for example, benzyl ethylether; the aldehydes include, for example, the linear alkanals having8-18 carbon atoms, citral, citronellal, citronellyloxy-acetaldehyde,cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; theketones include, for example, the ionones, α-isomethylionone and methylcedryl ketone; the alcohols include anethole, citronellol, eugenol,geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbonsinclude mainly the terpenes, such as limonene and pinene. Preference is,however, given to using mixtures of different fragrances which togetherproduce a pleasing fragrance note. Such perfume oils can also comprisenatural fragrance mixtures, is such as are obtainable from vegetablesources, e.g. pine oil, citrus oil, jasmine oil, patchouli oil, rose oilor ylang-ylang oil. Likewise suitable are muscatel, sage oil, camomileoil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil, lindenblossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oiland labdanum oil, and orange blossom oil, neroli oil, orange peel oiland sandalwood oil.

The fragrances can be incorporated directly into the compositionsaccording to the invention, although it may also be advantageous toapply the fragrances to carriers which enhance the adhesion of theperfume to the laundry and, as a result of a slower release offragrance, ensure long-lasting fragrance of the textiles. Cyclodextrinshave, for example, proven successful as such carrier materials, wherethe cyclodextrin-perfume complexes can also additionally be coated withfurther auxiliaries.

Inorganic Salts

Further suitable ingredients of the compositions are water-solubleinorganic salts, such as bicarbonates, carbonates, amorphous silicates,normal waterglasses, which do not have outstanding builder properties,or mixtures thereof; in particular, alkali metal carbonate and/oramorphous alkali metal silicate, primarily sodium silicate with a molarratio of Na₂O:SiO₂ of 1:1 to 1:4.5, preferably from 1:2 to 1:3.5, areused. The content of sodium carbonate in the end preparations is herepreferably up to 40% by weight, advantageously between 2 and 35% byweight. The content in the compositions of sodium silicate (withoutparticular builder properties) is generally up to 10% by weight andpreferably between 1 and 8% by weight. Fillers and extenders which maybe present are also, for example, sodium sulfate in amounts of from 0 to10% by weight, in particular 1 to 5% by weight, based on thecompositions.

EXAMPLES Example P1

In a 3-1three-neck flask fitted with stirrer, distillation attachmentand vacuum connection, 1 000 g (1.52 mol) of hydrogenated coconut oil,720 g (4.45 mol) of aminopropylmethylethanolamine (APMMEA) and 7 g ofhypophosphoric acid were mixed at 85° C. The mixture was heated to 180°C. and stirred at this temperature for 5 h, during which the water ofcondensation was continuously distilled off. Finally, the pressure wasreduced to 10 mbar in order to remove unreacted amine. Then, in a secondreaction vessel, 230 g (1.97 mol) of sodium chloroacetate were dissolvedin 670 ml of water at 85° C. To this solution were added, in portions,550 g (1.78 mol) of the amidoamine prepared previously, the pH beingmaintained between 6 and 9. The mixture was then heated to 90° C. andstirred at this temperature for 5 h, where, toward the end of thereaction, sodium hydroxide was added in order to keep the pH constant.The betaine was obtained as a yellowish-transparent liquid which had adry residue of 51.3% by weight. The active substance content was 44.0%by weight, the content of NaCl was 7.7% by weight.

Example P2

Analogously to Example P1, 632 g (2.05 mol) of the amidoamine obtainedas intermediate were dissolved in 98 g of isopropyl alcohol at 60° C.Then, 245 g (1.94 mol) of dimethyl sulfate were added to the mixture inportions with stirring, during which the temperature was maintainedbetween 60 and 70° C. over 4 h. The amide quat was obtained as a viscousliquid with an active substance content of 90% by weight.

The table below gives a number of formulation examples.

TABLE 1 Cosmetic preparations (water, preservatives add to 100% byweight) Composition (INCI) 1 2 3 4 5 6 7 8 9 10 Texapon ® NSO — — — — —— 38.0  38.0  25.0  — Sodium Laureth Sulfate Texapon ® SB 3 — — — — — —— — 10.0  — Disodium Laureth Sulfosuccinate Plantacare ® 818 — — — — — —7.0 7.0 6.0 — Coco Glucosides Plantacare ® PS 10 — — — — — — — — — 10.0 Sodium Laureth Sulfate (and) Coco Glucosides Betaine as in Ex. P1 — — —— — — 5.0 5.0 10.0  4.0 Amide quat as in Example P2 2.0 2.0 2.0 2.0 4.04.0 — — — — Eumulgin ® B2 0.8 0.8 — 0.8 — 1.0 — — — — Ceteareth-20Eumulgin ® VL 75 — — 0.8 — 0.8 — — — — — Lauryl Glucoside (and)Polyglyceryl-2 Polyhydroxystearate (and) Glycerin Lanette ® OB 2.5 2.52.5 2.5 3.0 2.5 — — — — Cetearyl Alcohol Cutina ® GMS 0.5 0.5 0.5 0.50.5 1.0 — — — — Glyceryl Stearate Cetiol ® HE 1.0 — — — — — — — 1.0 —PEG 7 Glyceryl Cocoate Cetiol ® PGL — 1.0 — — 1.0 — — — — — Hexyldecanol(and) Hexyldecyl Laurate Cetiol ® V — — — 1.0 — — — — — — Decyl OleateEutanol ® G — — 1.0 — — 1.0 — — — — Octyldodecanol Nutrilan ® Keratin W— — — 2.0 — — — — — — Hydrolyzed Keratin Lamesoft ® LMG — — — — — — 3.02.0 4.0 — Glyceryl Laurate (and) Potassium Cocoyl Hydrolyzed CollagenEuperlan ® PK 3000 AM — — — — — — — 3.0 5.0 5.0 Glycol Distearate (and)Laureth-4 (and) Cocamidopropyl Betaine Generol ® 122 N — — — — 1.0 1.0 —— — — Soya sterol Highcareen ® GS 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 Betaglucan Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Chitosan Copherol ® 12250 — — 0.1 0.1 — — — — — — Tocopherol AcetateArlypon ® F — — — — — — 3.0 3.0 1.0 — Laureth-2 Sodium Chloride — — — —— — — 1.5 — 1.5 (1-4) hair rinse, (5-6) hair treatment, (7-8) showerpreparation, (9) shower gel, (10) washing lotion

1-10. (canceled)
 11. A quaternary surfactant of the formula (I),

wherein R¹CO is a linear or branched, saturated or unsaturated,optionally hydroxy-functionalized acyl radical having 6 to 22 carbonatoms and 0, 1, 2 or 3 double bonds, R² is a CH₂COOH radical, an alkylradical having 1 to 4 carbon atoms, a CH₂CH₂OH or a CH₂CH₂OCH₂CH₂OHgroup, and X is halide, alkyl sulfate, alkyl carbonate or alkylphosphate.
 12. The quaternary surfactant of claim 11, wherein R² is aCH₂COOH radical.
 13. The quaternary surfactant of claim 11, wherein R²is an alkyl radical having 1 to 4 carbon atoms, a CH₂CH₂OH or aCH₂CH₂OCH₂CH₂OH group.
 14. A process for the preparation of quaternarysurfactants of the formula (I),

wherein R¹CO is a linear or branched, saturated or unsaturated,optionally hydroxy-functionalized acyl radical having 6 to 22 carbonatoms and 0, 1, 2 or 3 double bonds; R² is a CH₂COOH radical, an alkylradical having 1 to 4 carbon atoms, a CH₂CH₂OH or a CH₂CH₂OCH₂CH₂OHgroup, and X is halide, alkyl sulfate, alkyl carbonate or alkylphosphate, comprising the steps of: (a) forming a fatty acid amidoamineby reacting a fatty acid and/or a fatty acid glycerol ester and anaminopropylmethylethanolamine; and (b) quaternizing the fatty acidamidoamine with an alkylating agent.
 15. The process of claim 14,wherein the fatty acid is a compound of the formula (II)R¹CO—OH  (II) wherein R¹CO is a linear or branched, saturated orunsaturated, optionally hydroxy-functionalized acyl radical having 6 to22 carbon atoms and 0, 1, 2 or 3 double bonds.
 16. The process of claim14, wherein the fatty acid glyceride is a compound of the formula (III)R¹CO—CH₂CH(OR³)CH₂OR⁴  (III) wherein R¹CO is a linear or branched,saturated or unsaturated, optionally hydroxy-functionalized acyl radicalhaving 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds; each of R³and R⁴ is independently hydrogen or optionally hydroxy-functionalizedacyl radicals having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.17. The process of claim 14, wherein the reaction mixture in step (a) isfurther comprised of a dicarboxylic acid.
 18. The process of claim 14,wherein the alkylating agent is chloroacetic acid and/or a salt thereof.19. The process of claim 14, wherein the alkylating agent is an alkylhalide, a dialkyl sulfate, a carbonate, a phosphate or ethylene oxide.20. A cosmetic preparation comprising a compound of claim
 11. 21. Apharmaceutical preparation comprising a compound of claim 11.